Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C19/00—Acyclic saturated compounds containing halogen atoms
  • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
  • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
  • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C211/15—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
  • C07C43/04—Saturated ethers
  • C07C43/12—Saturated ethers containing halogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
  • C07C43/04—Saturated ethers
  • C07C43/13—Saturated ethers containing hydroxy or O-metal groups
  • C07C43/137—Saturated ethers containing hydroxy or O-metal groups containing halogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/003—Esters of saturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/62—Halogen-containing esters
  • C07C69/65—Halogen-containing esters of unsaturated acids
  • C07C69/657—Maleic acid esters; Fumaric acid esters; Halomaleic acid esters; Halofumaric acid esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/004—Surface-active compounds containing F

Definitions

• the present invention relates to novel compounds having fluorinated end groups, their use as surface-active
• Fluorosurfactants whose static surface tension is very low (16-18 mN / m), can be used in a wide variety of applications and have e.g. for improved wetting of surfaces. So they are e.g. used as an interface mediator or emulsifier or viscosity reducer in paints, varnishes or adhesives.
• WO 03/010128 describes perfluoroalkyl-substituted amines, acids, amino acids and thioether acids which have a C 3-2 o-perfluoroalkyl group. From JP-A-2001/133984
• New compounds have now been found which are suitable as surface-active substances and preferably one or more of the above-mentioned.
• a first object of the present invention are compounds of formula (I) (R f -A a -C c) n- (spacer) m -X 0 (I) wherein
• R f CF 3 -CF 2 -CF 2 -O-CF (CF 3 ) -CH 2 - > CF 3 -CF 2 -CF 2 - or CF 3 -CF 2 -CF 2 -O- CF (CF 3 ) -CO-,
• R ' H or alkyl
• n 1, 2, 3, 4, 5 or 6
• the hydrocarbon units of the spacer of the compounds of the formula (I) may be aliphatic or aromatic units optionally provided with heteroatoms.
• the moiety is (R f -A a -C c) n in the surface-active compounds thereby to a saturated, branched or unbranched hydrocarbon moiety, preferably a saturated, branched or unbranched alkylene group, wherein one or more carbon atoms to nonadjacent by O or N, preferably O, may be replaced, bound.
• a hydrocarbon unit containing preferred heteroatoms is a polyethylene or polypropylene glycol unit.
• the grouping (R f -A a -C c) n is used in the surface-active compound prior to multiple, preferably twice or three times. In another variant of the invention the grouping (R f A a -C c) n is used in the surface-active compound only once.
• R '' ' is preferably H or alkyl, in particular C 1 -C 4 -alkyl.
• R f CF 3 -CF 2 -CF 2 -O-CF (CF 3 ) -CH 2 -,
• n 1, 2, or 3
• n 0 or 1, preferably 1,
• R " is H or C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl.
• Rf may also be CF 3 -CF 2 -CF 2 - se.
• C O.
• the compounds of the formula (I) preferably contain two or three Rf groups.
• Rf CF 3 -CF 2 -CF 2 -0-CF (CF 3) -CH 2 is
• R ' H, CH 3 , C 2 Hs
• X is an anionic, cationic, nonionic or amphoteric group
• R 1 hydrogen or -CH 2 -COO- (A) a -Rf
• R 2 hydrogen, -CH 2 -COO- (A) a -Rf or X
• R 'and R have the meanings described for formula (I), in particular the preferred meanings described.
• D and / or D 'are equal to H or X, where at least one group must be equal to X when R " H or alkyl.
• X is preferably an anionic, cationic, nonionic or amphoteric group, p and q are preferably independent 1-4, in particular 1-2, are preferred ..
• Rf in formula (III) is CF 3 -CF 2 -CF 2 -O-CF (CF 3 ) -CO-
• R ' is H or Aikyl, preferably CH 3 or C 2 H 5 ,
• C alkylene, preferably C1 alkyl, or O,
• X is an anionic, cationic, nonionic or amphoteric group, spacer has the meanings described for formula (I), in particular the preferred meanings
• a 0 or 1, preferably 1, and
• Rf may also be CF3-CF2-CF2-.
• X is a hydrophilic group, preferably an anionic, cationic, nonionic or amphoteric group.
• a preferred anionic group X can be selected from -COO "- S0 3", -OSO3 "-PO3 2", -OP0 3 2 ⁇ - (OCH 2 CH 2) s -0- (CH 2) t -COO " ,
• s is an integer in the range of 1 to 000
• t is an integer selected from 2, 3 or 4
• w is an integer selected from 1, 2 or 3.
• Preferred anionic groups include in particular -
• anionic groups include -SO 3 " , -OSO 3 " , -PO 3 2 " , or OPO 3 2" .
• a sulfonate group -SO 3 " is preferred
• R is H or Ci -4 alkyl at any position
• R 1, R 2 and R 3 are each independently alkyl -30 H, Ci,
• Ar is an unsubstituted or mono- or polysubstituted
• substituted aromatic ring or fused ring systems with 6 to 18 C atoms, in which also one or two CH groups can be replaced by N.
• the preferred cationic groups include in particular -NR R 2 R 3 + Z ' and
• each of these groups may be preferred per se.
• a preferred non-ionic group may be selected from: linear or branched alkyl, wherein one or more non-adjacent carbon atoms replaced by O, S, and / or N are replaced, -OH, -SH, -0- (glycoside) 0 s
• u is an integer from the range of 1 to 6, preferably 1 to 4 o 'is an integer from the range of 1 to 0,
• the preferred non-ionic groups include in particular linear or branched alkyl, wherein one or more non-adjacent C atoms are replaced by O, S and / or N, -OH and -0- (glycoside) 0 '.
• a preferred amphoteric group may be selected from the functional groups of the acetyldiamines, the N-alkylamino acids, the N-alkylaminosulfonic acids, the betaines, the sulfobetaines, or
• M is H or an alkali metal ion, preferably Li + , Na + or K + :
• Particularly preferred compounds according to the invention are those which as hydrophilic group X one of the preferred anionic groups, the preferred non-ionic groups or the preferred
• compounds which contain the groups -SO 3 " , -OSOy, -PO 3 2" or OPO 3 2 " polyethylene glycols or polypropylene glycols, -CH (OH) -CH 2 -NH- ⁇ , -Y- (CH 2 -CH 2 ) 2 -CH 2 -O) v -R 4 , betaines, or sulfobetaines
• Preferred counterions here are Na + , K + and NH 4 + , in particular Na +, particularly preferred are: -SO 3 " , polyethylene or polypropylene glycols, Sulfobetaines, the group -CH (OH) -CH 2 -NH-Sach and the group -Y- (CH 2 -CH 2 -O) v -R 4 .
• Particularly advantageous compounds with X -S0 3 ⁇ .
• Particularly advantageous compounds of the formula (I) are those in which one or more of the variables have the preferred meanings.
• Particularly advantageous compounds of the formula (I) are those in which all the variables mentioned have the preferred meanings.
• Preferred examples of the formula (IV) are compounds of the formulas (IV-1) to (IV-8), where R 'has the meaning described for formula (IV), in particular the preferred meanings:
• w 0-10, preferably 1-3
• the compounds of the formula (II) according to the invention can preferably be prepared by esterification of maleic acid and aconitic acid or their
• Formula (VII) represents the presence of Z / E double bond isomers.
• the compounds according to the invention can also preferably be prepared by esterification of malic acid and citric acid with one or more alcohols of the formula (V) and subsequent functionalization of the hydroxy groups to introduce the group X.
• the alcohols used are commercially available and / or their
• the synthesis of succinates or tricarballylates according to the invention is preferably carried out in a two-stage synthesis via the corresponding maleates or hydroxysuccinates or the corresponding aconite or
• the introduction of the group X is then carried out by addition to the double bond or derivatization of the OH group according to methods familiar to the person skilled in the art.
• Esterification catalysts can be used. These mentioned syntheses are described in WO 2010/149262, WO 201 1/082770 and WO 20/084118. The disclosures in the cited references are hereby also expressly incorporated into the disclosure of the present application.
• Diaminoolefins are e.g. from the corresponding halides
• Metathesis can be symmetric or asymmetric
• Dicarboxylic acid ester olefins are produced, which can be converted by aminolysis and subsequent reduction in suitable starting materials.
• Advantages of the compounds according to the invention may be in particular: a surface activity which is equal or superior to conventional hydrocarbon surfactants in terms of efficiency and / or effectiveness - biological and / or abiotic degradability of the substances without formation of persistent perfluorinated degradation products such as PFOA
• the compounds according to the invention preferably have a particular surface activity.
• the compounds of the formula (I) according to the invention, in particular the compounds of the formula (II), can be significantly improved over the fluorosurfactants of the prior art
• a second object of the present invention is the use of the compounds according to the invention and the preferred embodiments described above as surfactants,
• Fluorosurfactants of the formulas (II), (III) and (IV) are preferably used, in particular the said particularly preferred compounds.
• the mixtures according to the invention may also contain solvents, additives, auxiliaries and fillers and non-fluorinated surfactants.
• solvents include silicone particles, plasticizers and surface-modified pigments
• Preferred fields of use are, for example, the use of the fluorosurfactants according to the invention as additives in preparations for
• Surface coating such as paints, varnishes, protective coatings,
• Photoresists, top antireflective coatings, bottom antireflective coatings) or in optical applications eg photographic coatings, Coatings of optical elements
• agrochemicals e.g for polishes and waxes, eg for furniture, floors and automobiles, in particular in floor polishes, in fire extinguishing agents, lubricants, in
• Immersion photolithography method e.g. in developer solutions
• Additive preparations for the addition of appropriate preparations.
• the compounds useful according to the invention as surfactant for washing and cleaning applications, as well as for use as additives / surfactants in cosmetic products such.
• Hair and body care products e.g., shampoos, hair conditioners and hair conditioners
• foam baths e.g., creams or lotions having one or more of the following functions: emulsifiers, wetting agents,
• the fluorosurfactants according to the invention for application are usually incorporated in appropriately designed preparations. Usual use concentrations are 0.01 - 1.0 wt .-% of
• Surfactants of the invention based on the total preparation.
• agents containing the fluorosurfactants according to the invention are likewise provided by the present invention.
• Such agents preferably contain a carrier suitable for the respective intended use, as well as optionally further active ingredients and / or optionally adjuvants.
• Preferred agents are colored and
• Preferred agents are dyestuff and lacquer preparations and printing inks.
• water-based paint formulations that are the
• Fluorosurfactants according to the invention alone or in admixture with additives, subject of the present invention. It is preferred to use lacquer formulations based on the following synthetic film formers: polycondensation resins such as alkyd resins, saturated / unsaturated polyesters, polyamides / imides, silicone resins; Phenol resins; Harn Stoff resins and melamine resins, polyaddition resins such as polyurethanes and epoxy resins, polymerization resins such as polyolefins, polyvinyl compounds and
• fluorosurfactants according to the invention are also suitable for use in paints based on natural substances and modified natural products. Preference is given to lacquers based on oils, polysaccharides such as starch and cellulose and also based on natural resins such as cyclic
• Oligoterpenes Oligoterpenes, polyterpenes and / or shellac.
• the fluorosurfactants according to the invention can be used both in physically curing (thermoplastics) and in crosslinking (elastomers and duromers) aqueous coating systems.
• the fluorosurfactants according to the invention preferably improve the flow and
• fluorine surfactants to be used according to the invention mentioned here are the subject matter of the present invention.
• fluorosurfactants for the purposes mentioned is the
• Drying tube, dropping funnel and thermometer are 30 ml absol.
• Et 2 0 present and enter via a septum 70 ml of 1 M LiAlH 4 solution (0.07 mol) in Et 2 0th
• In the dropping funnel are 44.30 g (0, 12 mol) of methyl Perfluoro (2-methyl-3-oxahexanoate) (ABCR, Düsseldorf Germany) in 50 ml absol.
• Reaction process creates a turbid dispersion.
• the batch is cooled in an ice bath.
• the decomposition of the excess LiAlH 4 is carried out by adding 10 ml EtOAc with slight heat of reaction.
• 10 g of H 2 0 are added, whereupon a flaky aluminum hydroxide precipitate is formed.
• 78 g of 25% strength sulfuric acid are added dropwise to the suspension over the course of 30 minutes, giving a clear two-phase mixture.
• the organic phase is separated and the aqueous phase washed with 3x 40 ml Et 2 0.
• the organic phases are combined, washed with 3x 40 ml H 2 0 and dried over Na 2 S0 4 .
• the ether is distilled off and the residue is fractionally distilled.
• Product 31, 8 g (bp 57 ° C / 100 mbar); Purity 91% (GC-MS); Yield 73% of theory
• reaction mixture is mixed with 25 ml of half-concentrated hydrochloric acid and MTBE and the phases are separated.
• the aqueous phase is extracted with 2x25mL MTBE and the combined org. Phases are washed with 1 ⁇ 30 ml of water and 1 ⁇ 30 ml of saturated NaCl solution and dried over sodium sulfate. The solvent becomes removed in vacuo at 400mbar and 40 ° C and the residue fractionally distilled.
• reaction time 24-48 h The reaction is monitored by TLC monitoring (reaction time 24-48 h). It is mixed with deionized water and the phases separated.
• Example 4 Synthesis of sulfosuccinates exemplified by sodium 2- sulfo-succinate bis [2- (2,3,3,3-tetrafluoro-2-heptafluoropropyloxypropoxy) ethyl] ester
• Reflux stirred It is mixed with 70mL of water and extracted with 3x50mL MTBE. The combined organic phases are washed with 1 ⁇ 50 ml of water and saturated NaCl solution and dried over sodium sulfate. The solvent is removed on a rotary evaporator.
• the static surface tensions ⁇ of aqueous surfactant solutions with different concentrations c (grams per liter) 0 are determined.
• Measuring method used Measurement of the surface tension with the Wilhelmy plate method according to DIN EN 14370.
• the surface or interfacial tension of the surfactant solution is calculated from the force acting on the wetted length of a plate according to the following formula.
• the plate consists of roughened platinum and is therefore optimally wetted, so that the contact angle ⁇ is close to 0 °.
• the term cos ⁇ therefore reaches approximately the value 1, so that only the measured force and the length of the plate must be taken into account.
• Pmax maximum pressure
• p density of the fluid
• h immersion depth
• r radius of the capillary

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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Detergent Compositions (AREA)
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• Inks, Pencil-Leads, Or Crayons (AREA)

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• 2013
  • 2013-07-16 EP EP13739612.3A patent/EP2874737B1/fr not_active Not-in-force
  • 2013-07-16 JP JP2015521993A patent/JP6392753B2/ja not_active Expired - Fee Related
  • 2013-07-16 US US14/416,003 patent/US9481643B2/en not_active Expired - Fee Related
  • 2013-07-16 WO PCT/EP2013/002112 patent/WO2014012661A1/fr not_active Ceased
• 2018
  • 2018-06-07 JP JP2018109197A patent/JP2018193373A/ja active Pending

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